Casein solution



Patented Dec. 3,1935

UNITED STAT -S PATENT.

2,023,389 oasanv sow'non can ladinrasiauii Island, N; rzjr to The:Muralii Company, Inc., a corporation of New York No'Dra wing.Application December s, 1933,

No. 701,572 33 Claims. (Cl. 134-50) lil In! in various industrialprocesses, such as the manufacture of water paste paints," water-oilemulsiona'glues, sizes; insecticides, etc. My improved casein solutionis also especially suitable for the preparation of coating compositionsl5. adapted to be .applied to walls/floors, leather,

' paper, etc. It may also be used for the. production of so-calledwater-emulsion paste paints and;

serve as a basic'in'gredient of printing inks.

A third object of my p is subsequently rendered slightly acidic orslight;- ly alkaline and which; simultaneously retains its usefulproperties for relatively-long periods of time.

I A fourth object to! this invention is the preparation of a casein soluon of heavy body yet at the same time having 8 flowing. properties.

l A fifth object of the present invention is the V 30, manufacture of analmost neutral casein solution without employing alkalis during itsproduction,

thus savings in costs and simplifying operations.

-. The basic idea-of the present inventionis to a casein'solution bypeptizing and/or dissolving casein at elevated temperatures by j meansof soluble fluorides in the'presence of flne--' 'ly dividedsilica and'aregulated quantity of water. Whentheprocessis carried'out inthisinan-'40 her, the casein see'mato'melt or dissolveto pro-.

1 duce ayerysmooth viscous solution and it does 1 i not appear tothrough a curdy stage. De

Y pending upon ratios of the'ingredients used,

' the finished casein solution has a'lowor high 45. viscosity its'reactlonjmayj be either. slightly- .basic .or acidic,- -"Ihe iinished'product may be dilutedto extentlqr renderedjslightiy alkawithoutadversely changing or losing its valuable properties, the higher pHvalues being 501 in general conducive tohigher visco'sities. I havefound ,by experimentation that. solubl fluoi'ldes'senerallfl may bealthough I prei new use fluorides of the alkali 'metalsf"and .oi'-Sodium 'fluoridealoneorin withfammoniuln fluoride-is especially valu em;invention is'ui 20. production of a casein sol tion which will remainstable regardless of'wheth'erthis solutionable for--the aforementioned-While I prefer to use thesecompoundslfor'economic reasons, I do notintend to limit mi -invention to the use of these compounds,-since anysoluble fluor-' V ide may be employed which will produce soluble 5caseinate's. Soluble fluorldesfii liave found, when used in accordancewith my improved process, have the property of dissolving or' peptizingcasein, partially. neutralizing the same andsimultaneously of making thesame resistant. to lay-'10 drolysis and to attack by variousmicroorganisms,

It is to be noted that these'agents alone, with I .out requiringadditional reagents, willbring about the production of "stable caseinsolutions. .Al-

though prefer toyuse sodium or ammonium .15 fluorides or mixtures ofcompounds in; amounts varying-from 5'to 20 parts perof commercial.-acld-prcipitated casein, other ra'tios will produce satisfactoryresults.

The water to be added during the reaction-may 2 0 vary to a largeextent; i.- e.,- I may merely moisten e the casein or add enough waterto prepare direct- .ly athin casein solution.'- I have found that the.best results, are obtained'hy using to 500 f p lirtsv of water periOO'parts of casein. ,I'hese 26'; quantitieso'f, water produce pasteswhich are easy to heat and handle andvyet will not become too I wish topoint out-that-my process is not limited to'the exact amounts ofsetforth above, since reasonable variations in water 'conto tent willnot adversely affect the final product, I have, furthermore, found thatthe presence of silica in the reacting compounds-permits the productionofcasein solutians at lower temperaa 'tu'res than heretofore possible.when thiamin as ture, is'vwarmed, the grainy mass starts to'bef come.pasty at temperatures ranging from-120: to F. depending prd'portionsofwa-.

tel-and other ingredients As a rule, the 1 smaller the-amounts of waterhigher to.

are the temperatures required pas y mass- Alth usfl. s s ctol'r o ut onsf temporary valuemay; be prepared at these low I-prefer to temperaturestansingfrom fio." r. to 210 It. suchegsolu- 4}; tions.'nptonlythavaluable gluelike-properties desired hutalso good stabilitywith to in particulan lhavefound that soli'i;

@tions ep ed-at 1mm": 180 F. to I". are by smooth- '0 understood,however, that the temperatl'lres may be varied-between wide limitswithout deletedth i p inventioncovers 129 1!. to 219985,

2 I 7 r n. and that from 1'10" F. to 210' r. is preferred only of thelonger life and greater stability 'of the solutions prepared within thisrange; Y Y 6 I have found by experimentation that any type 'of silicamaybe employed,.provided it-is-present in reasonably active form.Crystalline silicas or wise, which bringabout the desired results in myprocess.

I have found that the presence of silica in the reacting substances isessential and that almost neutral solutions of casein may be obtained,in this manner upon heating. The following 'table deplots the effect ofsilica-in the composition:

Without mum With'silica Casein Sodium fluoride... Ammonium fluorideSilica- Water, initial amount 125 paria Water for dilution.. 275 partspH of flnal solution 6.3 Appearance; Not smooth--- Q It is to be notedthat any type of acid-precipitated casein may be .used in. this process,such as muriatic, sulphuric-and lactic caseins.

' r r Example To 100 parts or commercial. acid-precipitated casein areadded-150 parts of water, 14 parts of sodium fluoride; parts of ammoniumfluoride and '7 parts; of pulverized silica. The mixture is stirred tohomogeneity, and'after standing long enough to thoroughly soak thecasein particles, is

and maintained at this temperature for periods of time varying from afew moments to several hours.

During this treatment, the casein will change its mass has been changedfrom a coarsely granular" mass to 'a smooth, stifl paste, 300 parts ofwater at 120". F. are added, whereupon the mixture will have a-'temperature somewhat below 195 E, say 6 about 160 F., at whichtemperaturethe dilution can be completed under continuous stirring. ThisI latter temperature is not of particular. importance, although I preferto dilute the mass while still warm since casein becomes more viscous 70on cooling and difficult to thin to the degree desired. It is'advisableto avoid too high temperatures, for example 210 F-.; since the continuedapplication of such temperatures may cause darkening of the solution."The pH of the finished 76 product which has. employed ,a sulphuricacidaoaas so" fore; that this invention clearly covers any form ofheated to 195 F. under continuous,- slow stirring times ofcookingvarying from 55 hour. to 1 hour precipitated casein willbe about6.9-7.0. The sov lution, however, may be rendered alkaline by theaddition of suitable modifying agents such as borax, ammonium hydroxide,sodium silicate, trisodium phosphate or piperazine, that is com- 5pounds which will produce soluble caseinates. After the solution hasbeen completed, it is allowed to cool to room temperature. I wish toemphasize that the solution and stabilization of the'casein is broughtabout during the initial heating stage and. not by subsequent dilutionwhich is carried out merely for the purpose 5 V of adjusting theflnished'product to a proper consistency. 'I may also vary thecharacteristics of the casein solution by using fluorides in combina- 16tion with other electrolytes. A combination, of sodium fluoride withammonium chloride gives {very satisfactory results, although othercompounds may be substituted for ammonium chloride. By increasing theproportions of sodium 20 fluoride and silica, products may be made whichare alkaline in reaction although no alkali was used in the process; Myinvention is not restricted tothetemperatures, percentages or otherexemplary data given.' 2i! except as governed by the appended claims.

I'claim: v 1.-The process of producing a. casein solution comprisingreacting casein in the presence of heat, water, and a soluble fluorideselected from 80 the group consisting of alkali metal fluorides andammonium fluoride and finely divided silica and subsequently dilutingthe reaction product with water.

2. The process of producing a casein solution 88 comprising reactingcasein in the presence of .heat, water, and a, soluble fluoride selectedfrom the group consisting of alkali metalfluorides and ammonium fluorideand amorphous-silica and subsequently diluting the reaction product with40 I water.

3. The process of producing a casein solution characterized by itsstability and undiminished viscosity over long periods of timecomprising heating casein in .the presence of water, a soluble fluorideselected from the group consisting of alkali metal fluorides andammonium fluoride and flnely divided silica to temperatures of l70-210E. and subsequently diluting the reaction product with water.

4. The process of producinga casein solution characterized by itsstability and undiminished viscosity over long periods of timecomprising heating casein in the presence of a soluble fluoride selectedfrom the group consisting of alkali metal fluorides and ammoniumfluoride and amorphous silica to temperatures of 170-210' F.

5. The process of producing a casein solution comprising reacting in thepresence of heat about .100 parts of casein with about 125-500 parts ofwater, 5-30 parts each of a soluble fluoride selected from the groupconsisting ofalkali metal fluorides and ammonium fluoride and silica.

6. The process of producing a casein solution characterized by itsstability and undiminished viscosity over long periods of timecomprising heating about parts ofcasein with about to 500 parts ofwater, 5 to 30 parts each'of a solubl'efluoride selected from the groupconsisting of alkali metal fluorides and ammonium fluoride and silica,to a temperature of -210 F.

7. The process'of producinga casein solution a a sa divided silica andthe reaction product with water.

8. The process oi producing a, casein solution comprising reactingcasein and ammonium fluorl de-in the presence oi heat, water, and finelydi-1 vided silica andsubsequentlydiluting the reaction productrwithwater:

9. The process oi -producing a casein solution characterized by itsstability and undiminished viscosity overlongperiods .01. timecomprising heating casein in the presence of .water, an

metal fiuorideand finely divided silica to .temper'atures or 180 to 195F. and subsequently diluting the reaction product-with water.

10. The process 01' producing a caseimsolution finely divlded's ilica totemperatures 01 180 to 195F. "1 w J 11; The process. 01' producing a.casein composition characterizedby its stability and undiminishedviscosity over long periods of time comprising-reacting casein and asoluble fluoride selected from the group consisting of alkalimetalfluorides and ammonium fluoride, finely divided amorphous silica andwater" at temperatures of 170 to 12.- The' process of producing [acasein composition characterized by its stability ,andundimlnishedviscosity over long periods of time compris v ing reacting caseinand asoluble fiuorideselected and ammonium fluoride, inthe presence of heat,

amorphous silica and water.

13.- The process of producing a casein composition characterized by itsstability and undimin- -ished wiscosity over silica aud water. I

14. The procas of producing a casein solution characterized by itsstability and'undiminished viscosity over long periods of timecomprisingreacting casein and ammonium fluoride, finelydi-w vided silicaand water at temperatures oi- 1'10 to I 15. The process oi. producing acaseincornpo sition characterized by its stability and undiminishedviscosity over long periods of time compris ing heating casein in thepresence of a soluble fluoride selected from the group consisting 6ialkali metal fluorides and "ammonium fluoride,

finely" divided silica and water temperatures of 170" to 2'1-o- F:

16. The process of producing a casein compoposition characterized by itsstability and. undiminished viscosity over long periods of time com?prising reacting casein'and a, soluble fluoride selected from thegroupconsis'ting of alkali metal fluorides and ammonium' fluoride;finely divided at temperatures of: no in 210 F. l

' 17. The process or producing a casein solution silica, water and analkaline pHmodifying agent acting casein and a soluble fluoride selectedfrom ,thegronp consisting oi. alkali metal fluorides and ammoniumfluoride, finely divided silica, am-

sition by its stability long' of time com-' prising reacting casein andafluoride of an al; kali metal, in the presence of heat, finelydividedmoniuin'chloride and waterat temperaturesot minishedvisco'sityover long of timecom prising heating casein in the presenceof a solu.ble fluoride selected irom the group consisting of alkali metalfluorides and ammonium fluoride, finely divided silica. an alkalinepH-modiiying 5 agent and water to temperatures 01 170' to 210 F. 19. Theprocess or producing a casein solution characterized by its stabilityand, undiminished' viscosity over long periods of time comprisingheating casein in the presence oi a soluble fluoride 10 selected i'romthe group consisting 'oi'alkali metal group consisting, of alkali metalfluorides and ammonium fluoride, finely divided silica and vwat'er.

casein, a soluble fluoride selected-from the group:

consisting of alkali'metal fluorides and ammonium fluoride and finelydivided silicareacted in the presence of water, I

22. Anew composition of matter'comprising I casein. a soluble fluoride'selectediror'n the group consisting of alkali/metal fluorides andammonium fluoride, and amorphous silica reacted in the; presence ofwater. \a 23. A new composition oi. mattercomprising V casein, acombination of soluble fluorides selected; from the group consistingoi-alkali metal fluorides from the group consisting of alkali metalfluorides and ammonium fluoride and finely divided silica reacted in thepresence of water.

- agent.

25. A new composition of matter comprising casein, an alkali metalfluoride and finely dividedsilica reacted inthe presence oi water. V 25.A' new composition, ofv matter .comprisingf cflein, ammonium fluorideand finely divided silica reacted in the presence otwa 27. A newcomposition of matter comprising casein;- sodium fluoride and finelydivided'silica 1 reacted in the presence or water. 28. The process ofproducing a caseincomposition comprising heating casein fin the presenceof 3 water, an alkali metal fluoride and finely divided silicaat atemperature in the range 180 to 195; l".

29. The process of producing a casein mrnpositiori comprising heatingcasein in the presenceof, water, an ammonium fluoride and finely divid-"ed silica ata temperature in the range 180to 195" F. v

' 30. The process ot'producing a casein composition comprisingheatingcasein in the presence of water,.an alkali metal fluoride, anammonium i fluoride and finely divided silica at a temperature in therange 170 to2101". V 31. The process of producing a casein compositioncomprising. heating casein in the presence or" water, a soluble-fluorideselected from the group consisting of alkali metal fluorides andammonium fluoride and finely divided silica to a temperature in therange @210" F. j

. 32. The method. of controlling the resista t pH of a compositioncomprising ca's'ein, a soluble fluoride selected from the'groupjcbnslsting of al-' 7 '21. A new, composition of matter comprising.kall metal flucrides aid ammonium flucride'and ,fluoride selected fromthe group consisting of "finely divided silica. reacted in the presence01 alkali metal 'fluoridescnd ammcnimn heat, comprising yaryln thequantity of silica. and flnely divided silica reacted in the 'prese tp Ia otheamccniprisingyaryingthe qufliwotdllcg.-

33. Th method of controlling the resultant present; 1 -5- pH of acomposition comprising casein, a soiublet I W 4 c'tli'ilrlcgmbfCORRECTION; t V 2mg; m5; 2,023,389. December'3. 1935.

C IL'IDDI NGSQ l! is heteby certified that} efrm ecpears in the'prihtdspecificaticdgcfthef nb ove" cugibcred pa tem requining correction asfollcws z Paze Z gSecOnEc Iumn. lines 2%30 gnd 36-37 lu s land-2respectively; su ike out the wcrds'and cqnima 3in tl 1 e' presence ofhea' t, Jwate'r," a nii insert the samehfti' .'f lucri.deiiIifiinesj'32fai1d' 39 respectively; page 3,, second colfi n. Iinefil'c l a im' 22. 2 strikzhhjxt the comma afteij "fl uoride";ilwii 1e 42,'c'laiihi 24, beginningwi'th .th'e word 'ch" strike o'ut'alltokind,includingi'fagent" ih'ii-he-Bpand inse'ttthe 'sc;he after "and"in like 41; strike outv the period at the "end oi line 4 v linsertfitheseine efler 'wate in line 42; a dihat' ihe'aid Lettersi'latent 's houldhe mm with these correctichs therein' magma smflm mommrct the recnrd ofthe-case in the Patent Office. Y

Sigiicdfand sealed pm; 17.111 dayofjDece nbelt A1 9. 1935."-

"(SQ-l) I n .h'lflinz Comissionei' dfiatentg'.

' .kall metal flucrides aid ammonium flucride'and ,fluoride selectedfrom the group consisting of "finely divided silica. reacted in thepresence 01 alkali metal 'fluoridescnd ammcnimn heat, comprising yarylnthe quantity of silica. and flnely divided silica reacted in the 'presetp I a otheamccniprisingyaryingthe qufliwotdllcg.-

33. Th method of controlling the resultant present; 1 -5- pH of acomposition comprising casein, a soiublet I W 4 c'tli'ilrlcgmbfCORRECTION; t V 2mg; m5; 2,023,389. December'3. 1935.

C IL'IDDI NGSQ l! is heteby certified that} efrm ecpears in the'prihtdspecificaticdgcfthef nb ove" cugibcred pa tem requining correction asfollcws z Paze Z gSecOnEc Iumn. lines 2%30 gnd 36-37 lu s land-2respectively; su ike out the wcrds'and cqnima 3in tl 1 e' presence ofhea' t, Jwate'r," a nii insert the samehfti' .'f lucri.deiiIifiinesj'32fai1d' 39 respectively; page 3,, second colfi n. Iinefil'c l a im' 22. 2 strikzhhjxt the comma afteij "fl uoride";ilwii 1e 42,'c'laiihi 24, beginningwi'th .th'e word 'ch" strike o'ut'alltokind,includingi'fagent" ih'ii-he-Bpand inse'ttthe 'sc;he after "and"in like 41; strike outv the period at the "end oi line 4 v linsertfitheseine efler 'wate in line 42; a dihat' ihe'aid Lettersi'latent 's houldhe mm with these correctichs therein' magma smflm mommrct the recnrd ofthe-case in the Patent Office. Y

Sigiicdfand sealed pm; 17.111 dayofjDece nbelt A1 9. 1935."-

"(SQ-l) I n .h'lflinz Comissionei' dfiatentg'.

